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1.
2-Alkyl-4-amino-5-(tert-butyl-NNO-azoxy)-2H-1,2,3-triazole 1-oxides: synthesis and reduction 总被引:1,自引:0,他引:1
V. P. Zelenov A. A. Voronin A. M. Churakov Yu. A. Strelenko V. A. Tartakovsky 《Russian Chemical Bulletin》2014,63(1):123-129
A new approach to the synthesis of 4-amino-5-(tert-butyl-NNO-azoxy)-2-R-2H-1,2,3-triazole 1-oxides 1 was developed. Compounds 1 were obtained by reactions of 3-amino-4-(tert-butyl-NNO-azoxy)furoxan with aliphatic amines RNH2 (R = Me, Et, Pri, Bu, and But). 4-Amino-5-(tert-butyl-NNO-azoxy)-2-tert-butyl-2H-1,2,3-triazole 1-oxide was transformed under the action of acids into 4-amino-5-(tert-butyl-NNO-azoxy)-1-hydroxy-1H-1,2,3-triazole. Methylation of the latter with diazomethane mainly involves the O atom of the triazole oxide ring. Reduction of compounds 1 gave 4-amino-5-(tert-butyl-NNO-azoxy)-2-R-2H-1,2,3-triazoles and 4-amino-5-(tert-butyldiazenyl)-2-R-2H-1,2,3-triazoles (R = Me, Pri, and But). The structures of the compounds obtained were confirmed by 1H, 13C, and 14N NMR spectroscopy. 相似文献
2.
O. A. Ivashkevich Vadim E. Matulis P. N. Gaponik G. T. Sukhanov J. V. Filippova A. G. Sukhanova 《Chemistry of Heterocyclic Compounds》2008,44(12):1472-1482
Quantum-chemical calculations have been carried out on molecular electrostatic potentials, proton affinity in the gas phase,
gas phase basicity, and pK
BH+ values in aqueous solution for C-nitro- and N-alkyl-4(5)-nitro-1,2,3-triazoles, and the relative stability of the isomeric
N-alkyl-4(5)-nitrotriazoles (alkyl = Me, Et, i-Pr, t-Bu) in the gas phase and in aqueous solution. For all the studied substances in the gas phase the 2H-tautomer and the N(2)-isomers
were considerably more stable than the corresponding N(1) compounds, and the 3H-tautomer and N(3)-isomer were the least stable.
In aqueous solution 1- and 3-isomers had close values of energies, but in the case of C-nitro-1,2,3-triazole the 1H form became
even more stable than the 2H-form. It was established which ring nitrogen atoms of 1,2,3-triazoles are protonated in the gas
phase and in solution. The obtained data correlate well with the results of experimental investigations on the alkylation
of 1,2,3-triazoles in acidic and basic media and of the experimental investigation on the alkylation of C-nitro-1,2,3-triazoles
with diethyl sulfate carried out in the present work.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1816–1828, December, 2008. 相似文献
3.
Enantiomerically pure and sterically-varied 2-organylapoisopinocampheylboranes (RapBH2; R=Me, IpcBH2; R=Et, EapBH2; Pr, PraBH2; i-Bu, i-BapBH2; R=Ph, PapBH2; and R=i-Pr, i-PraBH2) were prepared from their corresponding 2-organylapopinenes (2-R-apopinenes; R=Me, Et, Pr, i-Bu, Ph, and i-Pr) and the relative efficiency of these reagents for the asymmetric hydroboration of representative prochiral alkenes compared. With the exception of Ph, the results reveal simple relationships between the steric requirements of the groups R (Me, Et, Pr, i-Bu, Ph, and i-Pr) in these reagents and the moderate to excellent enantioselectivities achieved in the asymmetric hydroboration of six representative prochiral alkenes, such as 2-methyl-1-butene, cis-2-butene, trans-2-butene, 2-methyl-2- butene, 1-methyl-1-cyclopentene, and 1-methyl-1-cyclohexene. 相似文献
4.
Aza-Michael addition of 4-aryl-1H-1,2,3-triazoles to 2-cycloalken-1-ones has been studied in the presence of DABCO as organic base. The reactions were carried out in acetonitrile at room temperature to provide 2,4-disubstituted 2H-1,2,3-triazoles as major adducts and 1,4-disubstituted 1H-1,2,3-triazoles as minor adducts. Though the reaction times are longer (4–8 days), the two regioisomers were separated by using column chromatography and the adducts were obtained in very good to excellent combined chemical yields. The electron-rich and electron-poor substituents on aryl moiety of 4-aryl-triazoles could tolerate the reaction conditions to afford the title adducts. 相似文献
5.
A. A. Golovanov I. S. Odin V. V. Bekin A. V. Vologzhanina I. S. Bushmarinov S. S. Zlotskii Yu. L. Gerasimov P. P. Purygin 《Russian Journal of Organic Chemistry》2016,52(3):414-420
Huisgen reaction of (E)-1,5-diarylpent-2-en-4-yn-1-ones and (E)-1,5-diarylpent-1-en-4-yn-3-ones afforded 1-aryl-3-(5-aryl-1H-1,2,3-triazol-4-yl)prop-2-en-1-ones and 3-aryl-1-(5-aryl-1H-1,2,3-triazol-4-yl)-prop-2-en-1-ones, respectively. (E)-1-Aryl-3-(5-phenyl-1H-1,2,3-triazol-4-yl)prop-2-en-1-ones reacted with hydrazine hydrate and phenylhydrazine to give 72–93% of 4-(3-aryl-4,5-dihydro-1H-pyrazol-5-yl)-5-phenyl-1H-1,2,3-triazoles which underwent dehydrogenation on heating in boiling acetic acid with formation of the corresponding pyrazole derivatives. The molecular structures of (E)-3-phenyl-1-(5-phenyl-1H-1,2,3-triazol-4-yl)prop-2-en-1-one and 4-[3-(4-methylphenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-5-yl]-5-phenyl-1H-1,2,3-triazole were studied by X-ray analysis. 4-(3-Aryl-4,5-dihydro-1H-pyrazol-5-yl)-5-phenyl-1H-1,2,3-triazoles showed toxicity against Daphnia magna. 相似文献
6.
G. V. Sakovich G. T. Sukhanov Yu. V. Filippova A. G. Sukhanova K. K. Bosov 《Russian Chemical Bulletin》2013,62(1):111-116
Alkylation of 4(5)-nitro-1,2,3-triazole with alcohols in concentrated H2SO4 occurs at all three endocyclic N atoms, giving a mixture of isomeric N(1)-, N(2)-, and N(3)-alkyl-4-nitro-1,2,3-triazoles (alkyl is isopropyl, sec-butyl, and cyclohexyl). The selectivity of the alkylation depends on the alcohol used. The most selective alkylation is provided at the N(2) atom when isopropyl (81%) and sec-butyl alcohols are used (67%). With an increase in the reaction time, also in the order isopropyl-, sec-butyl-, and cyclohexyl-4-nitro-1,2,3-triazoles, the N(2)-isomers undergo isomerization into N(1)-alkyl-4-nitro-1,2,3-triazoles. In all the cases, the fraction of the N(3)-substitution products in the mixtures is 6–30%. 相似文献
7.
Norberto González-Mojica Leticia Almazán-Sánchez Jesús G. García-Torres Ivette Santana-Martinez Diego Martínez-Otero Miguel A. Sánchez-Carmona 《合成通讯》2019,49(5):679-687
A collection of 1,2,3-triazole-3-oxides was obtained from oxidation of the corresponding 1,4-disubstituted-1,2,3-triazoles mediated by a H2O2–CF3CO2H system through a simple protocol in good yields showing high efficiency. 相似文献
8.
An efficient two step synthetic methodology of new 5(4)-aryl-4(5)-[3(5)-(2-hydroxyphenyl)-1H-pyrazol-5(3)-yl]-1H-1,2,3-triazole dyads was established. The reaction of (E)-2-styryl-4H-chromen-4-ones, used as building blocks, with sodium azide, gave 4(5)-aryl-5(4)-(chromon-2-yl)-1H-1,2,3-triazoles bearing either electron-donating or electron-withdrawing substituents in their styryl moiety which upon reaction with hydrazine hydrate afforded the expected pyrazoles in moderate to very good yields. 相似文献
9.
This study develops a new efficient pathway for synthesis of 2,4-disubstituted 1,2,3-triazoles through regioselective direct arylation between 2-aryl-1,2,3-triazole N-oxides and Ar-B(OH)2. The reaction proceeds smoothly at room temperature and exhibits good yield and high C5 position selectivity. The possible pathway of oxidative Suzuki coupling is also discussed. This simple methodology can be used to construct 2,4-disubstituted 1,2,3-triazole moiety. 相似文献
10.
Mikhail V. Dubovis Gennady F. Rudakov Alexander S. Kulagin Kseniya V. Tsarkova Sergey V. Popkov Alexander S. Goloveshkin Georgiy V. Cherkaev 《Tetrahedron》2018,74(6):672-683
Based on the deoxygenation reaction of 1-(1-tert-butyl-3-nitroazetidine-3-yl)-1H-1,2,3-triazoles a new method for the synthesis of substituted 1-(1H-imidazole-4-yl)-1H-1,2,3-triazoles has been developed. Fungicidal activity of these compounds has been investigated at a range of phytopathogenic fungi. 相似文献
11.
Boris I. Usachev Sergey A. UsachevGerd-Volker Röschenthaler Vyacheslav Ya. Sosnovskikh 《Tetrahedron letters》2011,52(50):6723-6725
4-Aryl-6-(trifluoromethyl)-2H-pyran-2-ones and ethyl 4-aryl-6-(trifluoromethyl)-2-oxo-2H-pyran-3-carboxylates react with sodium azide to produce highly functionalized CF3-1,2,3-triazoles: 3-[5-(trifluoromethyl)-1,2,3-triazol-4-yl]cinnamic acids and monoethyl esters of [5-(trifluoromethyl)-1,2,3-triazol-4-yl]arylmethylidene malonic acids. 相似文献
12.
I. D. Kosenko I. A. Lobanova L. A. Chekulaeva I. A. Godovikov V. I. Bregadze 《Russian Chemical Bulletin》2013,62(2):497-503
An approach to the synthesis of new 1,4-disubstituted 1,2,3-triazoles, in which one or both substituents contain the cobalt bis(1,2-dicarbollide) fragment, was suggested based on the 1,3-dipolar cycloaddition of azides to alkynes catalyzed by copper(I) compounds. The reaction of cobalt bis(1,2-dicarbollide) azido derivatives with different terminal acetylenes led to 1,2,3-triazoles with the [((CH2)2X(CH2)2O-C2B9H10)Co(C2B9H11)] (X = O or CH2) substituent at position 1 and the organic substituent at position 4. The [3+2] cycloaddition reaction of cobalt bis(1,2-dicarbollide) alkynyl derivatives with methyl azidoacetate furnished isomeric 1,4-disubstituted 1,2,3-triazoles with the metallacarborane fragment at position 4. 1,2,3-Triazole with metallacarborane substituents at positions 1 and 4 containing 36 boron atoms was also synthesized. 相似文献
13.
Silvana Chiappetta Gianfranco Denti Jon A. McCleverty 《Transition Metal Chemistry》1989,14(6):449-453
Summary The syntheses of [MoL*(NO)(OR)NHC6H4NH2)], [MoL*(NO)I(NHC6H4NHMoL*(NO)(OR)] (L*=tris(3,5-dimethylpyrazolyl)borate; R=Me, Et,n-Pr,i-Pr,n-Bu and C5H11), and [{MoL*(NO)(OR)}2NHC6H4NH] (R=Me, Et andn-Pr) are described, the compounds being characterised by elemental analyses, i.r. and1H n.m.r. spectroscopy. 相似文献
14.
Three new N2S2 donor ligands 1,1′-((2-(2-(phenylthio)phenylthio)phenyl)methylene)bis(3,5-R-1H-pyrazole), R = H (LH), R = Me (LMe), R = i-Pr (Li-Pr) have been prepared and characterized. These bifunctional ligands incorporate two distinct chelate donor systems, by virtue of the presence of bispyrazole and bisthioether functions. The preferred conformation of these ligands is such that the N2 and S2 donor moieties may be oriented in opposite directions, thus favoring the formation of molecular chains when treated with AgBF4. The X-ray structures of Ag(I) complexes show that, depending on the steric hindrance present on the pyrazole rings, these ligands behave as κ4-SSNN-μ bridging tetradentate (when R = H), or κ3-SNN-μ bridging tridentate (when R = Me, i-Pr). Interestingly, [Ag(LH)]BF4 crystallizes in the chiral space group P41, with the molecular chain that is folded around the 41 screw axis. 相似文献
15.
Evangelia D. Chrysina Éva Bokor Kyra-Melinda Alexacou Maria-Despoina Charavgi George N. Oikonomakos Spyros E. Zographos Demetres D. Leonidas Nikos G. Oikonomakos László Somsák 《Tetrahedron: Asymmetry》2009,20(6-8):733-740
Per-O-acetylated β-d-glucopyranosyl azide was transformed into an intermediate iminophosphorane by PMe3 which was then acylated to N-acyl-β-d-glucopyranosylamines. The same azide and substituted acetylenes gave 1-(β-d-glucopyranosyl)-4-substituted-1,2,3-triazoles in Cu(I)-catalyzed azide–alkyne cycloadditions. Deprotection of these products by the Zemplén method furnished β-d-Glcp-NHCO-R derivatives as well as 1-(β-d-Glcp)-4-R-1,2,3-triazoles which were evaluated as inhibitors of rabbit muscle glycogen phosphorylase b. Pairs of amides versus triazoles with the same R group displayed similar inhibition constants. X-ray crystallographic studies on the enzyme–inhibitor complexes revealed high similarities in the binding of pairs with R = 2-naphthyl and hydroxymethyl, while for the R = Ph and 1-naphthyl compounds a different orientation of the aromatic part and changes in the conformation of the 280s loop were observed. By this study new examples of amide-1,2,3-triazole bioisosteric relationship have been provided. 相似文献
16.
In this study, a new methodology for the one-pot synthesis of 4-aryl-1H-1,2,3-triazoles from arylglyoxaldoxime semicarbazone is presented. 4-Aryl-1,2,3-triazoles were obtained in moderate to good yields via sodium dithionite and O2, which are all efficient, safe and inexpensive reagents. This reaction is more suitable for large-scale syntheses than those using hydrazoic acid, sodium azide, or organic azides. 相似文献
17.
Mariola Koszytkowska-Stawińska Ewa Mironiuk-Puchalska Tomasz Rowicki 《Tetrahedron》2012,68(1):214-225
2-Substituted-2H-1,2,3-triazolo-nucleosides with 3-phosphonopropyl, 2-hydroxyethyl, 2-cyanoethyl, carbamoylmethyl, or 1-deoxy-2,5-anhydro-d-mannitol-1-yl on the triazole N-2 nitrogen atom were obtained via the DBU-promoted N-alkylation of 3-(pivaloyloxymethyl)-1-[(NH-1,2,3-triazol-4-yl)methyl]thymine with diethyl 3-bromopropylphoshonate, 2-bromoethanol, acrylonitrile, methyl bromoacetate, or 3,4,6-tris(O-benzoyl)-2,5-anhydro-d-mannitol 1-tosylate. The N-2/N-1 regioselectivity of the alkylation varied from 57/43 (methyl bromoacetate) to 97/3 (diethyl 3-bromopropylphoshonate). The 1-substituted-1H-1,2,3-triazoles, when formed in the appreciated amount in the alkylation reaction, were converted into the corresponding 1-substituted-1H-1,2,3-triazolo-nucleosides. The substitution pattern of 2-substituted-2H-1,2,3-triazolo-nucleosides was confirmed by 1H–15N HMBC NMR spectra; the triazole nitrogen atoms were identified through their correlations with the triazole exo-cyclic protons. 相似文献
18.
The preparation of a number of 5-substituted 1-[2-(trimethylsilyl)ethoxy]methyl-1H-1,2,3-triazoles via reaction of 1-[2-(trimethylsilyl)ethoxy]methyl-1H-1,2,3-triazole with n-butyllithium followed by addition of various electrophiles is reported. Removal of the protecting group by action of diluted aqueous hydrochloric acid or by tetrabutylammonium fluoride in tetrahydrofuran leads to the appropriate 4-substituted 1H-1,2,3-triazoles. 相似文献
19.
L. V. Klyba N. A. Nedolya O. A. Tarasova E. R. Zhanchipova O. G. Volostnykh 《Russian Journal of Organic Chemistry》2010,46(7):1038-1048
The mass spectra of previously unknown 1-alkyl(cycloalkyl, aryl)-3-alkoxy(aryl)-2-methylsulfanyl-1H-pyrroles were studied. Fragmentation of all 3-alkoxy-substituted pyrroles under electron impact (70 eV) follow both ether
and sulfide decomposition paths; In particular, 1-R-substituted 3-methoxy-2-methylsulfanyl-1H-pyrroles (R = Me, Et, i-Pr, s-Bu, cyclo-C5H9, cyclo-C6H11, Ph) lose methyl radical group from both methoxy and methylsulfanyl groups. The mass spectra of 1-sec-butyl- and 1-cycloalkylpyrroles also contained a strong peak (10–49%) from odd-electron [M — C
n
H2n
]+· ion formed via cleavage of the N-R bond with synchronous hydrogen transfer. Cleavage of the O-Alk bond in the fragmentation
of 3-alkoxy-1-isopropyl-2-methylsulfanyl-1H-pyrroles (Alk = Et, i-Pr, t-Bu) was accompanied by rearrangement process leading to the corresponding alkene and odd-electron 1-isopropyl-2-methylsulfanyl-1H-pyrrol-3-ol ion. The main fragmentation path of 1-alkyl-2-methylsulfanyl-3-phenyl-1H-pyrroles (Alk = Me, i-Pr) under electron impact involves dissociation of the S-Me bond with formation of rearrangement 1H-[1]benzothieno[2,3-b]pyrrol-8-ium ion. 相似文献
20.
Helio G. Bonacorso Francieli M. Libero Fábio M. Luz Maiara C. Moraes Susiane Cavinatto Felipe S. Stefanello Melissa B. Rodrigues Nilo Zanatta Marcos A.P. Martins 《Tetrahedron letters》2017,58(40):3827-3830
This work reports the synthesis of a series of (1H-1,2,3-triazol-4-yl)carbohydrazides (2), which were obtained from 4-trichloroacetyl-1H-1,2,3-triazoles (1). Triazoles 1 were synthesized by 1,3-dipolar cycloaddition reaction, starting from 4-alkoxy-1,1,1-trichloroalk-3-en-2-ones and benzyl azides and easily (15 min) converted to 2 by reaction with hydrazine hydrate (73–82% yield). Carbohydrazides 2 proved to be a versatile building block for constructing a series of fluorinated heterocycles analogous to rufinamide, i.e., 1H-1,2,3-triazol-4-yl-1,3,4-oxadiazoles, a pyrrole derivative, and a 2-pyrazoline, through [4+1]–, [1+4]–, and [3+2]–cyclocondensation reactions, respectively. Finally, and according to the Lipinski’s rule of five, 2,6-difluorobenzylated 1,2,3-triazoles can be considered as potential candidates for further biological activity assays. 相似文献